Flameproofing composition



fiatented sept. 16, 1952 I llo Drawing. Application Nove Serial No. 57,822

7 Claims. (01. 106-15"?- 1 This invention relates tocompositions adapted to flameproof -combustible materials: such as .tex-, tiles-paper, artificial leather orthe like. By the termflameprcof is meant resistant to the suns port of aflameaf-terthe initiatingsourceof the flame is, withdrawn.

flhe' fiameproofing composition of my present invention provides a means for modifying .the

rateand temperature of evolution of hydrochloric acid from hydrochloric acid liberating organic materials by balancing inhibitors and metal oxides capable of forming oxychlorides at high temperatures to achieve a fiameproof complex at. the combustion temperature, and includes oneor more metallic oxides, a chlorinated material and an' inhibitor acting in this unique way with the chlorinated material. I have found", that my composition possesses efiec tive fiarneproofingproperties and is also water" insoluble in all its ingredients so that theflame-' proofness of the materialtreated with my composition is preserved despite weathering or re-'- peated laundering.

w I attributejthe flameproofing efiectiveness of my composition to its ability to form, metallic oXychloride-cellulose complexes when exposed to hydrochloric acid, liberated-by the chlorinated mater-ial;, -inz the presence of cellulose at combusti fi temn w esaaet that n i biw mbraces. peee smenis tempo-Swen Pl an important part; namely, it retardsthe .libera-' tion of hydrochloric acid'from the chlorinated materialiwhile the latter is heated an'duntil the temperature is reached at'wh'ich the complex is formed. Although I do-not wish to commit myself unnecessarily to any specific theory yet the foregoingexplanation seems to account for the unusual effectiveness of my composition as-con trasted with" several prior' compositions having ingredients similar to'mine. 1 i

it In addition to the three abovejdescribed ele-'- nients'of'my "composition, namely, the" metallicoxide: 'th'e'chlorinated' material and the inhibitor, my composition preierably also includes one or more metallic sa1ts"'o'f"weak inorganic acids, which-enhance? the flameproofing efiectiveness,

and also certain .amines, amides orf amine salts which greatly reduce after-glow,.asls very desirtendencyto mildew. 5

able in certainfieldsof .use, and also reduces the;

' In making myrcoinpositionfa" powder is first; made up of all the dry ingredients and the powder is thencompounded with thechlorinated material. Alternativelyf the powder "may be. com-- pounded with the chlorinated material by adding "Harry Hopkinson, Lawrenceville, N. .1

mber i, 1943, if;

each ofthe ingredients of the powder in turn to the chlorinated material. Ishall describe inidetail first: the powders and their ingredients and then the chlorinated materials.

A. The, powders include:

1; The metallic oxides, present in an amount ranging fromabojut. 40% to about 65 and preferably about f1 5%'ofthe weightof the powder. They consist preferably of zinc oxide, stannic oxide, lead oxide, magnesium oxide, ferric oxide, or mixtures thereof and also desirably other oxidesalone or in admixturesuchas the oxides of man antl fih molybdenum, tellurium, titanium, p r, chrom um. aluminum, vanadium and tungsten. a y 7 2. fine inhibitorsmay be inorganic, or metalloorganic. 'lheir function is apparently to retard the; liberation of hydrochloric acid from the chlorinated material while the latter is heated and until the temperature is reached at which the metallic oxychloride-cellulose complex is fbrmedythereby difiering in function from the conventional stabilizer employed merely to stabilize the chlorinated material against dehydroclil'orination during storage or use or under the influence of sunlight- 'i'heuse of quantities adequate for my purpose "is'important and the quantity is gauged by the amount of metallic oxide used. The quantity required is about 20% or over but'not over about l0 andpreferably about;

35% or "the weight "or theimletallicoxide. 1

"As such inhibitors I'prefer basic lead carbonate,

calcium silicate, leadsilic'a'te orlead sulfate but others may also be used, if in adequate quantities,

such as calcium stearatacalcium salicylate, calcium ethyl aceto-acetate, lead oleate, lead naphthenate, dibasic lead salt of stearic acid, and

other organo-metallic lead salts, strontium naph'-' than that ofiiamingcombustion and this problem is accentuated rather than-alleviated by many prior flameproofing [compounds which. lengthen rather than shorten the afterglow. Where that is a problem my composition in-' cludes a glow proofer present in an amount which should/be at least 10% and can rangeupwardly as high, as-50% or more of the total weight of the powder, depending on'the glow resistance desired,

' molybdatefzinc borataleadjborat Many amines and amides andvarious salts containing amine linkages are useful for this purpose. Particularly adapted for this use are the phosphates, borates, and silicates of the water-insoluble, long-chain amines, such, for instance, as octadecylamine phosphate, borate and silicate and rosin amine phosphate, borate I and silicate. I

Some of these materials; *r otablyi the resin amine Phosphate "and bo'rate impartthe further desirable property of mildew-proofness, and alsocontribute to the fiameproofness, as wellasthe elowproofness or my composition,

4. Metallic salts of weak organidacids' may also be used in quantities, ranging fifrom about.

the. metallic oxides in imparting fiameproofness.

The following represent some of the materials.

available for this purpose m ta n t n m-si nna a ma e um il a' e' Zin a iil in' .w la ent reer arrests, magnesium s'tannate"tin"tungstate tin 'iz ms ium silicate, and lead molybdate; U

i w n sxem sqi mix-tn i, 1115m powdersinade inaccordance with eregoing.

Wh'lc hfinthe presence of chlorinated' 'materials;

to about 25% and preferably. about l5 7 of the weight-of the powder, asthey supplement v 4 r final flameproofing solution, The hydrochlor'i acid required for the described reaction may be incorporated in several ways, (a) by grinding the powder in a chlorinated plasticizer such as chlorinated paraffin, chlorinated diphenyls or methyl pentachlor stearate, etc., (b) by using a chlorinated film-former in the final solution such-as chlorinated rubber, polyvinyl chloride, polychlo rstyrene, -etc: j(c) bymombipirrg both;

The usual procedure'ito dissolve the 'chlorinated resin in a solvent. To this solution is.

added a paste made by grinding the fiameprooiing. powder together with color pigments if' desiredinthe'chosenplasticizer.

:crAiSilDDlfi-flXfilllp of a flam nr fins so ution follows using chlorinated rubber as the filma-irorrner and chlorinated parafiln as the plas'ticizer,

Solution #1 i Parts by weight araffin. are stirr tqxt 'mp .un il ii jl z rt flemep a n s to ell is mate l- Powder #1,

jjilijc'hlorz'ndted materials and" compoubdifig V metholds. Thel powders are usually ground'in a plasticizer to form a paste. beiorei adding to 'the;

completely d olved nd t e owdergi i 1 ,e pund'finrelierably i a; hr e-I m l iwifi he ch o i ated; pa afii The su sspa e is tbenfstirred.tho hlylnm h hlpr fi df rubber solution and "more toluol added ;as previ ously determined'in order to" leav the desired added weight on thegoods. v The good are thenj dipped in this solution and therexcesssolutiqn re oved by any of. e usual means. Thev goods are then dried in any suitable. manner. V'With ape: p xima e added wei h the good wi b'ei o nd little ch nged i appea,ra ice and eel nd" will be found to meet allthe usual tests: icr' flameproofness ,iboth.fb9fore andaftergl e hin g r and laundering. i r r Other examples illustrating-f different ,fffllm-"- Polyvinyl smart-is Chlorinated parailin (7,0,%

The chlorinat d rubbe i ch o n ted Carbon black In certain cases, the actual solution of the resin is notnecessary as for instance. in the case of the application of vinyl resin by the organosol or plastisolmethod. In. this case the powder can be mixed directly with the organosols or plastisols and the whole mass fluxed on the goods to be treated.

The following is an illustration of the organosol type of flameproofing: V

i 1?a'rts by weight Vinylite resin vinyl 1 500 76 14 Powder #4 350 Methyl pentachlor s'tearate 300 Dioctyl phthalate 100 Mineral spirits .420

Xylol 180 The above are charged to a ball or pebble mill in any order andare allowed to grind until sufflciently well dispersed, usually 18 to 48 hours. The material is then ready for use and can be applied to the goods by any of the recognized methods, preferably by the conventional knifecoating technique. The degree of penetration into the cloth can be regulated both by the angle of the blade and by regulating the viscosity of the mixture. For good flameproofing results a high degree of penetration is desirable. In drying, the volatiles can be driven off in the ordinary ovens, but it is important that at some point in the drying cycle a temperature of 350 F. should be reached in order to melt the resin into a continuous film.

I claim:

1. A fiameproofing composition which includes a chlorinated organic material which releases hydrochloric acid when heated, at least one metallic oxide capable of reacting with hydrochloric acid in the presence of cellulose at combustion temperatures higher than at which the hydrochloric acid is normally liberated by the chlorinated material to form a flameproof compound, said metallic oxide being selected from the group consisting of oxides of zinc, tin, lead, magnesium, iron, manganese, molybdenum, tellurium, titanium, copper, chromium, aluminum, vanadium, and tungsten, an inhibitor adapted to retard the release of hydrochloric acid from the heated chlorinated material until the temperature is reached at which said reaction takes place, and a water-insoluble glowproofing material present in substantial quantities and consisting of a material selected from the group consisting of rosin amine phosphate, borate and silicate and octadecylamine phosphate, borate and silicate.

2. A flameproofing composition which includes a chlorinated organic material which releases hydrochloric acid when heated, at least one me- Ultramarine Monastral Blue tallic oxide capable of reacting-with. hydrochloric acid in the presence of cellulose at combustion temperatures higher than that at which-the hydrochloric acid is normally liberated bythechlorinated material to form a flameproof compound,

said metallic oxide being selected from the groupconsisting of oxides of zinc, tin, lead-magnesium,

iron, manganese, molybdenum, tellurium, tita: nium,,copper, chromium, aluminum, vanadium and tungsten, an inhibitor adapted to retard the release of hydrochloric acid from the heated chlos rmated material until the temperature is reached at whichsaid reaction takes place, and a waterinsoluble glowproofing material, present in subs stantial quantities and consisting of a salt of a long chain aliphatic amine-and a water insoluble mineral acid.

3. A flameproofi ng. coniDOSition which-includes a chlormatedorganic material which releases by:

drochloric acid when heated, at least one metallic oxide capable of reacting with hydrochloric acid in :the presence of cellulose at combustion tem:

peratures' higher than that at which the hydro-V chloric; acid is normally liberated by the chlorinated material toform a fiameproof compound,

said metallic oxide being selected from the group consisting of oxides of zinc, tin, lead, magnesium,

iron, manganese, molybdenum, tellurium, titanium, copper, chromium, aluminum, vanadium and tungsten, an inhibitor adapted to retard the, release of hydrochloric acid from the heated chlorinated material until the temperature isreached at which saidreaction takes place, se lected from the group consisting of basic lead carbonate, calcium silicate, lead silicate, lead sulfate, calcium stearate, calcium salicylate, cal-' cium ethyl aceto-acetate, lead oleate, lead naphthenate, dibasic lea-d salt of stearic acid, and other organo-metallic lead salts, strontium naphthenate, dibutyl tin maleate, and tetraphenyl tin, and a substantial quantity of at least one metallic salt of a weak inorganic acid selected from the group consisting of stannates, zincates, borates, silicates, molybdates, vanadates and tungstates of the metals zinc, antimony, magnesium, tin, lead and zirconium.

4. A powder for compounding with hydrochloric acid liberating chlorinated organic materials to form a fiameproofing composition which includes at least one metallic oxide, said metallic oxide being selected from the group consisting of oxides of zinc, tin, lead, magnesium, iron, manganese, molybdenum, tellurium, titanium, copper, chromium, aluminum, vanadium and tungsten, the total oxide being present in an amount of from about 40% to about 65% by weight of the dry solids and including substantial quantities of materials selected from the group consisting of zinc oxide, stannic oxide, magnesium oxide, lead oxide and ferric oxide, an inhibitor present in proportions of from about to about of the weight of the metallic oxide and selected from the group consisting of basic lead carbonate, calcium silicate, lead silicate, lead sulfate, calcium stearate, calcium salicylate, calcium ethyl acetoacetate, lead oleate, lead naphthenate, dibasic lead salt of stearic acid, and other organometallic lead salts, strontium naphthenate, dibutyl tin maleate, and tetraphenyl tin, a substantial quantity of at least one metallic salt of a weak inorganic acid selected from the group consisting of stannates, zincates, borates, silicates, molybdates, vanadates and tungstates of the metals zinc, antimony, magnesium, tin, lead and zirconium,

cale m slhizat eak an .zmmriium;

.n v .e ,93 Stan-t1 -quantmes 1 and COIISIStlIIg -of v v 1 f.

at least one metallic diiifiEfifiiimetailic oxide 135- ingaselecteddgom the group consisting of oxides oft-zinc gt i. m nesium, 1mm; manganesee yl enimi; ib lluiiiimn ti an mac pper; elirQ mium, aluminumflyanaidiflm anc l tungstgeng end -n.

a. waiter-insoluble glqwprovfing 'materiehpresent; in substantial quantities and consistinggofz 8.158111? of resinamineandaweakracid. V w 1 proofing... consisting, of substantial quantities? of e at least one. metallic. oxide, said meta l-limoxider being selected from .thegxtoupfionsis'tingwf oxides? of zinc, ..t1n, 1ead,., magnesium, iron; 3 manganese}; molybdenum, tellurium, titanium, copper,.chroaiuminuimivanad'ium: and: tungsten and a weteremsohible? glowproofing :zmaterial-spre'sentx in libsta'ntiail qum'ntit'iesand lconsistingmfi aes sflt of a: water insolublei alipliatie longvschatni'alh'inefj and-aimineral-ssieim o rHER REFERENcEs Reamend, American"lji estiirfin'eiierteh v61? 32'; e. 

3. A FLAMEPROOFING COMPOSITION WHICH INCLUDES A CHLORINATED ORGANIC MATERIAL WHICH RELEASE HYDROCHLORIC ACID WHEN HEATED, AT LEAST ONE METALLIC OXIDE CAPABLE OF REACTING WITH HYDROCHLORIC ACID IN THE PRESENCE OF CELLULOSE AT COMBUSTION TEMPERATURES HIGHER THAN THAT AT WHICH THE HYDROCHLORIC ACID IS NORMALLY LIBERATED BY THE CHLORINATED MATERIAL TO FORM A FLAMEPROOF COMPOUND, SAID METALLIC OXIDE BEING SELECTED FROM THE GROUP CONSISTING OF OXIDES OF ZINC, TIN, LEAD, MAGNESIUM, IRON, MANGANESE, MOLYBDENUM, TELLURIUM, TITANIUM, COPPER, CHROMIUM, ALUMINUM, VANDADIUM AND TUNGSTEN, AN INHIBITOR ADAPTED TO RETARD THE RELEASE OF HYDROCHLORIC ACID FROM THE HEATED CHLORINATED MATERIAL UNTIL THE TEMPERATURE IS REACHED AT WHICH SAID REACTION TAKES PLACE, SLELECTED FROM THE GROUP CONSISTING OF BASIC LEAD CARBONATE, CALCIUM SILICATE, LEAD SILICATE, LEAD SULFATE, CALCIUM STEARATE, CALCIUM SALICYLATE, CALCIUM ETHYL ACETO-ACETATE, LEAD OLEATE, LEAD NAPHTHENATE, DIBASIC LEAD SALT OF STEARIC ACID, AND OTHER ORGANO-METALLIC LEAD SALTS, STRONTIUM NAPHTHENATE, DIBUTYL TIN MALEATE, AND TETRAPHENYL TIN, AND A SUBSTANTIAL QUANTITY OF AT LEAST ONE METALLIC SALT OF A WEAK INORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF STANNATES, ZINCATES, BORATES, SILICATES, MOLYBDATES, VANADATES AND TUNGSTATES OF THE METALS ZINC, ANTIMONY, MAGNESIUM, TIN, LEAD AND ZIRCONIUM. 